Poly(ether-carbonates) and poly(ester-ether carbonates) have long been prepared by melt polymerization of monomers, which already contained ether linkages, with diphenyl carbonate. Such monomers are generally prepared by reacting ethylene oxide in the presence of a catalyst with a monomeric material containing one or more aromatic hydroxyl groups. The hydroxyl groups are converted to hydroxyethoxyl groups, and thus the monomers containing intraether groups are obtained. During the preparation of the monomer containing the intraether linkages, it is very difficult to carry out the reaction without converting all of the hydroxyl groups to hydroxyethoxyl groups and without some additional reaction with the hydroxyethoxyl groups to form short poly(ethylene oxide) linkages.
The monomers containing intraether groups may be polymerized or copolymerized in the melt with, for example, diphenyl carbonate and/or diphenyl esters of dicarboxylic acids to form poly(ether-carbonates) or poly(ester-ether-carbonates by conventional procedures. Solution polymerization of these monomers with, for example, phosgene or bis(chlorocarbonate)esters of diols, to prepare polymers gives products of relatively low molecular weight.
U.S. Pat. No. 2,628,945 discloses the foaming of fusible, organic macromolecular polymers using ethylene carbonate as a foaming agent. U.S. Pat. No. 3,224,983 discloses the foaming of synthetic thermoplastic polymers containing cyclic carbonate moieties, either chemically combined or admixed in the polymer, by heating in the presence of an "activator."
The preparation of poly(ether-carbonates) by reacting the bis(hydroxyethyl)ethers of aromatic diols with, for example, diphenyl carbonate (and, in some cases, an added diol to prepare copolymers) is well known to those skilled in the art. A homopoly(ether-carbonate) prepared by this method would have the following structure: ##STR1##
We are aware of no art which discloses the preparation of poly(ether-carbonate) homo- or copolymers from the monohydroxyethyl ether of an aromatic diol. Such a polymer would have the following structure: ##STR2##
Aqueous alkaline hydrolysis of polymers and analysis of the hydrolysate by gas chromatography is a good method for determining the structure of polymeric materials. When structure (A) is hydrolyzed, the following diol specie is found: EQU HO--CH.sub.2 --CH.sub.2 --O--Ar--O--CH.sub.2 CH.sub.2 OH
Aqueous alkaline hydrolysis and chromatographic analysis of the hydrolysate of the poly(ethercarbonates) of this invention indicate a mixture of diol moieties are present. For example, when equimolar (one mole/repeat unit) amounts of cyclic ethylene carbonate and bisphenol A polycarbonate are reacted according to the process of this invention, and the polymeric product is hydrolyzed and analyzed by gas chromatography, the diol moieties found are:
__________________________________________________________________________ Diol Specie Mole % (CC) __________________________________________________________________________ ##STR3## 35.6 ##STR4## 49.9 ##STR5## 14.5 __________________________________________________________________________
Japanese Pat. No. 46-6973 (1971) discloses the preparation of poly(ester-ethers) by reaction of polyesters of aromatic diols with ethylene carbonate, but poly(ester-ether-carbonates) are not disclosed. Also, this patent does not disclose the desirable property of improved solubility which is a characteristic of applicants' invention. Our work indicates poly(ester-ethers) are less soluble in common organic solvents, such as methylene chloride, than are poly(ester-ether-carbonates) at the same level of ether(ethyleneoxy) modification.
It is well known to those skilled in the art that poly(ester-ether-carbonates) can be prepared by heating the bis(2-hydroxyethyl)ether of an aromatic diol or diols with, for instance, diphenyl carbonate and diphenyl terephthalate/isophthalate to eliminate phenol. However, we are not aware of any art which discloses poly(ester-ether-carbonate) compositions containing the moiety derived from the mono-2-hydroxy-ethyl ether of an aromatic diol. Aqueous alkaline hydrolysis of polymers and analysis of the hydrolyzate by gas chromatography is a good method for determining the structure of polymeric materials. Analyses of the aqueous alkaline hydrolyzate of the poly(ester-ether-carbonates) of the invention indicate a substantial amount of the mono-2-hydroxyethyl ether of the aromatic diol.
The present invention provides new poly(ester-ether-carbonate) compositions. The present invention also provides a process for preparing these polymers and a process for foaming aromatic diol polycarbonates and poly(ester-carbonates). The objects of the invention are accomplished by heating an aromatic diol polycarbonate or poly(ester-carbonate) with ethylene carbonate at about 160.degree. C. up to about 300.degree. C. (partial pressurization required to prevent loss of ethylene carbonate at high temperatures) for up to 5-6 hours, optionally in the presence of a suitable catalyst. The reaction may be represented as follows: ##STR6## wherein a+b+c=n and are not blocked as depicted but are randomly repeated, Ar is defined as aryl having 6-30 carbon atoms, R, R.sub.1, R.sub.2 and R.sub.3 are each ##STR7## wherein Ar' is aryl of 8 to 16 carbon atoms, and ##STR8## is present in amounts of greater than 0 to less than 100% and ##STR9## is present in amounts of more than 0 to less than 100%.
According to the present invention, there is provided a composition of matter comprising repeating units of: ##STR10## such as to result in an I.V. of about 0.05-2.00 of said composition and Ar, R.sub.1, R.sub.2, R.sub.3 and Ar' are as defined above.
In the particular embodiment claimed in the present invention, R is a mixture of greater than 0 to less than 100% ##STR11## and greater than 0 to less than 100% ##STR12## In applicants' copending application Ser. No. 760,801 filed 7/31/86, R is 100% ##STR13## In Japanese Pat. No. 46-6973 (1971) insofar as it relates to this invention, R is 100% ##STR14## However, it is not disclosed in this Japanese patent that R may be ##STR15## When R is ##STR16## or at least sometimes ##STR17## certain advantages such as lower Tg and melt viscosity (therefore improved processability) and improved solubility in common solvents are realized. Thus, compositions containing repeating units (2) above wherein R is at least sometimes ##STR18## are believed to be novel.
This invention also provides foamed structures, films, and fibers comprising the compositions described above. The new compositions of this invention provide molded products of good stiffness characteristics, higher elongation, good solubility, and processability is improved due to lower melting temperatures and lower glass transition temperature.
In the composition described structurally above, a, b, and c are at least 1 and usually 2 or more. The integers a, b, and c may range upwardly to result in molecular weights of processable compositions. When a, b, and c are too large, the compositions are not processable, because the molecular weights are so high as not to permit melting or dissolving. When a, b, and c are small, i.e., about 1, the compositions are useful as polyols for forming coating compositions. The terminal groups are hydroxy groups.
The I.V. (inherent viscosity) of the compositions may range from about 0.05 to about 2.00, preferably about 0.1 to about 0.7.
Ar may be substituted or unsubstituted. Conventional substituents may be used, e.g., alkylene, alkyl, aralkyl, or aryl group of 1 to 24 carbon atoms, halogen, etc.
The polymers of the invention are prepared by heating a mixture of an aromatic (as defined above) diol polycarbonate, poly(ester-carbonate) or copolymers thereof with ethylene carbonate at about 160.degree. C. up to about 300.degree. C. for a few seconds to 2-3 hours or more, depending on the molar ratio of ethylene carbonate/polycarbonate or poly(ester-carbonate), the melting or flow point thereof, the thermal stability thereof, and the circumstances or method of carrying out the reaction. The molar ratio of ethylene carbonate:polycarbonate or poly(ester-carbonate) may be about 0.005-1.9:1. However, where a foamed product is to be made, the ratio should be about 0.005-0.04:1. Excess ethylene carbonate (above 1.9:1 up to about 5:1) may be used in the process, but the excess ethylene carbonate above the 1.9:1 ratio must be removed, such as by vacuum distillation, before polymerization is completed. The excess ethylene carbonate in such a case would act as a solvent. Higher molar ratios require shorter reaction times. If the melting or flow point of the polymer is high, obviously longer reaction times will be required unless the reaction temperature is increased. Optionally, a catalyst may be added to increase the rate of the reaction. The reaction is usually carried out at or slightly below the boiling point of ethylene carbonate (248.degree. C.), but the reaction may be carried out at higher temperatures under pressure to prevent loss of ethylene carbonate. In general, the time of reaction varies indirectly with the molar ratio of ethylene carbonate/polycarbonate or poly(ester-carbonate) and the reaction temperature. The reaction may be carried out in a batch or continuous reactor (used with higher molar ratios of ethylene carbonate/polycarbonate or polyester-carbonate in which a foamed product is not desired), an extruder (for extruded shapes in which the carbon dioxide by-product of the reaction is utilized as a blowing agent), or an injection molding machine (for molded shapes in which the carbon dioxide by-product of the reaction is utilized as the blowing agent). Conventional extrusion-foaming and foam molding equipment may be used. Generally, extrusion foaming and foam molding operations are carried out at relatively low molar ratios of ethylene carbonate/polycarbonate or polyester carbonate (about 0.005 to about 0.04), since the amount of by-product carbon dioxide needed for these processes is small. Density reductions of 40-50% or more can be achieved at molar ratios of about 0.01/1-0.02/1.
For those instances in which an unfoamed product is desired, the reaction is carried out in a batch or continuous reactor under conditions which will allow the by-product carbon dioxide to escape without causing the reaction mixture to foam out of the reactor. Generally, the reaction is carried out until the theoretical volume of carbon dioxide has been evolved, and vacuum is applied for a short period to remove volatile materials. If the presence of small amounts of volatiles is acceptable, application of vacuum is not required to obtain useful polymers.
Since the rate of reaction is considerably dependent on the molar ratio of ethylene carbonate/polycarbonate or polyester-carbonate (faster rates at higher ratios), it is at times advantageous to begin the reaction at a higher than desired molar ratio of ethylene carbonate/polycarbonate or polyester-carbonate and apply vacuum to remove the excess ethylene carbonate when the desired theoretical volume of carbon dioxide has been evolved. This is especially true when polymers having high flow points or excessively high melt viscosities are utilized in the reaction. In such cases, molar ratios of up to 5 or more may be used in the starting reactants, but the ratio in the polymeric mixture must be no greater than 1.9:1 (ethyleneoxy:repeat unit of aromatic diol). The poly(ester-ether-carbonate) compositions of the invention contain 0.005-1.9 moles of ethyleneoxy(--O--CH.sub.2 --CH.sub.2 --) per repeat unit of aromatic diol polycarbonate or polyester-carbonate. The polymers containing low levels of ethyleneoxy are usually foamed compositions.
Although the reaction proceeds readily in the absence of added catalyst, it may at times be advantageous to add a catalyst or promoter to the reaction to increase the rate of reaction, particularly at relatively low molar ratios of ethylene carbonate/polycarbonate. Suitable catalysts and promoters include tertiary amines, quaternary ammonium and phosphonium salts, alkali metal salts, and compounds or polymers containing at least one unsubstituted amide hydrogen atom: ##STR19##
Aromatic diol polycarbonates which may be used to prepare the new compositions of the invention include all aromatic diol polycarbonates or copolycarbonates which are sufficiently thermally stable to withstand the conditions of the reaction and which are molten or substantially dissolved during the process. Aromatic diol, in this case, refers to any moiety to which are attached, directly to an aromatic ring, two hydroxyl groups. The hydroxyl groups may be on the same or different rings. The preferred polycarbonate is bisphenol A polycarbonate. The aromatic diol polycarbonates may be high or low I.V. The I.V. of the final polymer is usually somewhat lower than that of the aromatic diol polycarbonate. The I.V. of the aromatic diol polycarbonate should be about 0.05-0.2 if the poly(ether carbonate) product is to be used as a polyol. If the poly(ether carbonate) product is to be used as a molding plastic, the I.V. of the aromatic diol polycarbonate should be greater than 0.2, and preferably greater than 0.5.
Aromatic diol poly(ester-carbonates) which may be used to prepare the new compositions of the invention include all aromatic diol or copoly(ester-carbonates) which are sufficiently thermally stable to withstand the conditions of the reaction and which are molten or substantially dissolved during the process. They may contain greater than 0 to less than 100 mol % carbonate linkage and greater than 0 to less than 100 mol % moieties derived from at least one aromatic dicarboxylic acid containing 8-10 carbon atoms. Examples of suitable aromatic dicarboxylic acids include terphthalic, isophthalic, 2,6-naphthalenedicarboxylic, 4,4'-oxydibenzoic, 4,4'-biphenyldicarboxylic, and 4,4'-sulfonyldibenzoic acids. The aromatic diol poly(ester-carbonates) may be high or low I.V., but I.V.'s of about 0.3 to about 0.8 are preferred. Aromatic diol, in this case, refers to any moiety to which they are attached, directly to an aromatic ring, two hydroxyl groups. The hydroxyl groups may be on the same or differnt rings. The preferred poly(ester-carbonates) of the invention contain, in addition to the carbonate, bisphenol A, terephthalate, and isophthalate moieties.
The new polymers of the invention have utility as fibers, molding plastics, and films. They exhibit improved processability (due to depression of the glass transition temperature) and improved solubility in common solvents while maintaining high flexural moduli, relative to their aromatic diol polycarbonate or poly(ester-carbonate) precursors.
If desired, inert additives such as nucleating agents may be added before reaction of the ethylene carbonate with the aromatic diol polycarbonate or polyester-carbonate, particularly when the polymer is to be extrusion foamed or foam molded.
The following examples are submitted for a better understanding of the invention. Inherent viscosities of the polymers are determined at 25.degree. C. in a 40/25/35 weight mixture of p-chlorophenol/phenol/1,1,2,2-tetrachloroethane at a concentration of 0.1 g/100 mL. Films are pressed in a Hannafin press at 10.degree.-30.degree. C. above the melting or flow point of the poly(ether-carbonate) or poly(ester-ether-carbonate). H NMR data are obtained with a JEOL JNM-MH-100 nuclear magnetic spectrometer using d-trifluoroacetic acid as a solvent. Foamed moldings are carried out in a Newbury molding machine by the "short-shot" procedure, and unfoamed moldings are carried out in a Watson-Stillman (1/8-ounce) molding machine. For gas chromatographic analysis, the samples are first hydrolyzed in 1N KOH in n-propanol. The hydrolysate is then silated and separated on a column containing 10% silicone F-50 at 100.degree.-240.degree. C. Glass transition temperatures (Tg's) are determined with a Perkin-Elmer DSC-2 differential scanning calorimeter. For determining the properties of molded specimens, ASTM D638 is used for tensile properties, ASTM D790 is used for flexural properties, and ASTM D955 is used for heat-deflection temperature.